Process for breaking petroleum emulsions



Patented July 18', 1944 PROCESS FOR BREAKING PETROLEUM EMULSIONS MelvinDe Groote, University City, and Bernhard Keiser,

Webster Groves,

Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a

corporation of Delaware No Drawing. Application June 15, 1942, SerialNo. 447,165

8 Claims.

This invention relates primarily to the resolution of petroleumemulsions.

ly-occurring waters or brines dispersed in a more or less permanentstate throughout the oil which constitutes the continuous phase of theemulsion.

Another object is to provide an economical and rapid process forseparating emulsions which have been prepared under controlledconditions from-mineral oil, such as crude petroleum and relatively'soft waters or weak brines.

tion under the conditions just. mentioned is of significant value inremoving impurities, particularly inorganic salts, from pipeline oil.

We have discovered that if one oxyalkylates glycerol so as to introduceat least three oxyal- -kylene radicals for each hydroxyl group, and ifthe product so obtained is reacted with a polybasic carboxy acid havingnot over eight carbon atoms, and in such a manner as to yield afractional ester, due to the presence of at least one free carboxylradical, one canthen esterify said acidic material or intermediateproduct with at least one mole of an alcoholic compound of the typeherein described to give a variety of new compositions of matter whichhave utility in the demulsification of crude oil.

The compoundsherein contemplated may be produced in any suitable manner,but are usually manufactured by following one of two general procedures.In one of said procedures the oxyalkylated glycerol, which is, inessence, a polyhydric alcohol, is reacted with a polybasic acid so ts togive an acidic material or intermediate product, which, in turn, isreacted with an alcoholic body of the kind hereinafter described, andmomentarily indicated by the formula R1(0H)m. Generically, the alcoholicbody herein contemplated may be considered a member of the class inwhich m may vary from 1 to 10, although the specific signficance of m inthe present instance will be hereinafter indicated. The second procedureis to react an alcohol of the formula type R1 OH)m with a polybasic acidso as to produce an intermediate product, and then react saidintermediate product or fractional ester with the selected oxyalkylatedglycerol.

Controlled emulsification and subsequent demulsifica-' Glycerol may beconveniently indicated by the following formula:

0H Calla- OH on If treated with an oxyalkylating agent, and momentarilyconsideration will be limited to an oxyethylating agent, one may obtainan oxyethylated glycerol of the following formula type:

a KDn'H CaHsOr-hHiQh'H (CaHiCDuH in which the value of n may vary from 3to 10 and all the values of n need not be identical. If a polybasiccarboxy acid be indicated by the formula:

coon

' cool:

then the acyclic reaction product of one mole of oxyethylated glyceroland one mole of a polybasic carboxy acid may be indicated by thefollowin formula:

(clmo .'ooon coon CsHsOa-(CzHtOhiH clrnon n in which n" has thevalue ofone or two. Similarly, if two moles of the polybasic acid be used, thenthe compound may be indicated by the following formula:

o,Hlo ,.'oocR(c0on CzHr0r-(C:H40),u00CR(COOH),.-

clmown Likewise, if three moles of a polybasic acid are employed, thecompound may be indicated by the following formula:

o,mo oooa coon CaH Oa(O:H|O).. OOCR(CO0H),. (CrH4O),.'0OCR(C0OH)'-" If afractional ester of the kind exemplified by the three preceding formulasis reacted with one or more moles of an alcohol of the kind previouslydescribed in a generic sense of R1(0H) m,

.HCl gas, a dried sulfonic acid, or thelike.

using one or several procedures. 1 is to passan inert dried gas throughthe mass then obviously, one may obtain a material of the type indicatedby the following formula:

inwhichzvisl), lor2,yis0,lor2,andzis 1,2 or 3, and :c' is or 1, and y is1 or 2.

It has been previously stated that compounds of the type hereincontemplated may be obtained by oxyalkylating agents, without'being'limited to ethylene oxide. Suitable oxyalkylating agents includeethylene oxide, propylene oxide,-butylene ter so that the process isessentially self-esterifloxide and glycid, which, although not included,

strictly speaking, by the unitary structure CnI'IZnOv is included withinthe meaning of thehereto appended claims and may be simply considered asa variant of propylene oxide, i. e., hydroxypropylene oxide. hydrogenatom appears, it maybe replaced by metal, an ammonium radical, orsubstituted ammonium radical, or b an organic group derived from analcohol, such as an aliphatic alcohol, an aralkyl alcohol, or analicyclic alcohol. It may also be converted into an amide, including apolyarninoamide. may be rewritten in its broader scope, as follows:

in which n replaces the numbers 2, 3 or 4, Z includes the acidichydrogen atom itself. above formula, and hereafter for convenience, R1is intended to include any hydroxyl groups that remain.

If the compounds herein contemplated are obtained under usualconditions, at the lowest temperatures, then the monomeric form is mostlikely to result.

Similarly, Where a carboxylic.

Thus, the preceding formula In theof the recognized hydrophileproperties of the re- The production of the compoundsherein contemplated is the result of one or more esterification steps. As is wellknown, esterification procedures can be carried out in various manners,but generally speaking, esterifications can be carried out at the lowestfeasible temperatures by One" procedure to be esterified, and havepresent at the same time a small amount of a catalyst, such as driedAnother and better procedure, in many instances, is

to employ the vapors of a suitable liquid,so as to remove any waterformed and condense both the vapors of. the liquid employed and thewater in such a'manner as to trap out the'water and return the liquid tothe reacting vessel. This procedure is commonlyv employed in the arts,and for convenience, reference is made to U. S. Patent No. 2,264,759,dated December 2, 1941, to Paul c.

Jones.

Referring again to the last two formulas indicating the compound underconsideration, it can be readily understood that such compounds, innumerous instances, have the property of polyfunctionality. In view ofthis fact, where there .is at least one residual carboxyl and, at leastone cation. Thus, strictly speaking, the polymeric compounds are notabsolutely isomers of the' monomeric compounds, but since, for allpractical purposes, they can be so indicated, and since such practice iscommon in the arts concerned with materials of this type, it is soadopted here. Thus, reference in the appended claims to polymers isintendedv to include the self-esterification products of the monomericcompounds.

In view of what has been said, and in view curring oxyalkylene linkages,particularly the. oxyethylene linkage, it is apparent that the materialsherein contemplated may vary from compounds which are clearlywater-soluble through self-emulsifying oils, to materials which are balsam-like and sub-resinous or semi-resinous in nature. The compounds mayvary from monomers to polymers, in which the unitary structure appears anumber .of times, for instance, 10 or 12 times. i. e., truly insolublematerials of a hard plastic nature, are not herein included. In otherwords, the polymerized compoundsare soluble to a fairly definite extent,for instance, at least 5% in some solvents, such as water, alcohol,benzene,

dichloroethyl ether, acetone, cresylic acid, acetic.

acid, ethyl acetate, dioxane, or the like. This is simply another way ofstating that the polymerized product contemplated must be of thesubresinous type, which is commonly referred to as an A resin, or' a Bresin, as distinguished from a C resin, which is a highly infusible,insoluble resin (see Ellis, Chemistry of Synthetic Resins (i935), Pages862, et seq.) j Reviewing the form as presented, it is obvious that onemay obtain compounds within the scope disclosed, which contain neither afree hydroxyl nor a free carboxyl group, and one may also ob- 'tain acompound-of the type in which there is We are aware that compoundssimilarto those contemplated in the present instance may be derived frompolyhydroxylated compounds having more than three hydroxyl groups. Forinstance,

they may be derived from acyclic diglycerol, triglycerol, tetraglycerol,mannitol, sorbitol, pentaerythritol,

various hexitols, dulcitol, sorbitan, mannitan, dipentaerythritolmonoether, and other similar com- It is to be noted that true resins,

In the hereto appended claims the 'mixed polyglycerols,

alkylation and then employed in the same mannor as oxyalkylatedglycerol, as employed in the present instance, are not contemplated inthis specific case, although attention is directed to the same.

Reference is also made to other oxyalkylated compounds which may be usedas reactants to replace oxyalkylated glycerol, or oxyalkylated ethyleneglycol, which latter reactant is described in a co-pending applicationhereinafter referred to. The reactants thuscontemplated include the typein which there is an amino or amido nitrogen atom. Particularly, whenpresent in a low molal type of compound prior to oxyalkylation,

reference being made to polyhydroxylated materials, including thosehaving two or three by.- .droxyl groups, as well as those having morethan three, hydroxyl groups. For instance, the oxyalkylated derivatives,particularly the oxyethylated derivatives of ethyldiethanolamine,bis(hydroxyethyllacetamide, the acetamide oftris(hydroxymethyhaminomethane, tetrahydroxylated ethylene diamine, etc.Compounds may also be derived from cyclic diglycerol and the like.

Furthermore, for convenience, attention is diduced into .a singleglycerol molecule.

rected to a somewhat similar class of materials which are. described inour co-pending application Serial No. 401,381, filed July '7, 1941, nowPatent.

No. 2,324,493 dated July 20, 1943. Said co-pending application involvesthe use of the same type of alcoholic bodies for reactants, but islimited,

' among other things, to the compounds which are essentially symmetricalin nature, for instance, involving the introduction of two alcoholicresidues, whereas, in the present instance, one, two, or three, or more,might be introduced.

As indicated previously, the polybasic acids employed are limited to thetype having not more than eight carbon atoms, for example, oxalic,malonic, succinic, glutaric, adipic maleic, and phthalic. Similarly, onemay employ acids such as fumaric glutaconi'c, and various others, suchas citric, malic, tartaric, and the like. The selection of theparticular tribasic or dibasic acid employed, is usually concernedlargely with the convenience of manufacture of the finished ester, andalso the price of the reactants. Generally speaking, phthalic acid oranhydride tends to produce resinous materials, and greater care must beemployed if the ultimate or final product be -of a sub-resinous type.Specifically, the preferred type of polybasic acid is such as to containsix carbon atoms or less. Generally speaking, the higher the temperatureemployed, the easier it is to obtain large yields of esterlfled product,although polymerization may be stimulated. Oxalic acid may becomparatively cheap, but it decomposes readily at slightly above theboiling point of water. For this reason it i more desirable to use anacid which is more resistant gravity of 1.383.

The ethylene oxide is added in relais made to derivatives obtained byoxyethylation, although, as previously pointed out, other oxyalkylatingagents may be employed.

As far as the range of oxyethylated glycerols employed as reactants isconcerned, it is our pref erence to employ those in which approximatelyOXYETHYLATED GLYCEROL Example 1 184 pounds of glycerol is mixed with/2%, by weight, of caustic soda solution having a specific The causticsoda acts as a catalyst. tively small amounts, for instance, about 44pounds at a time. The temperature employed is from 150-180 C. Generallyspeaking, the gauge pressure during the operation approximates 200pounds at the maximum, and when reaction is complete, drops to zero, dueto complete absorption of the ethylene oxide. When all the ethyleneoxide has been absorbed and the reactants cooled,

a second small portion, for instance, 44'more pounds of ethylene oxide,are added and the proto pyrolysis. Similarly, when a polybasic acid isavailable in the form of an anhydride. such anhydride is apt to producethe ester with greater ense'than the acid itself. For this reason,maleic anhydride is particularly adaptable, andnalso everything elseconsidered, the. cost is comparatively low on a per molar basis, eventhough somewhat'higher on a per pound basis. Succinic acid or theanhydride has many attractive qualities of maleic anhydride, and this isalso true of adipic acid. For purposes of brevity, the bulk of theexamples, hereinafter illustrated, will refer to the use of maleicanhydride, although it is understood that any other suitable polybaslcacid may be employed. Furthermore, reference cedure repeated until thedesired ratio of 15 pound moles of ethylene oxide to one pound mole ofglycerol is obtained. This represents 660 pounds of ethylenepxide for192 pounds of glycerol.

OXYETHYLATED GLYCEROL Example .2

The ratio of ethylene oxide is increased to 18 pound moles for eachpound mole of glycerol. Otherwise, the sameprocedure is followed as inExample 1, preceding.

OXYETHYLBTED GLTCEROL Example 3 The same procedure is followed as in thetwo previous examples, except that the ratio of ethylene oxide toglycerol is increased to 21 to one.

OXYETHYLATED GLYcERor. MALEATE Example 1 One pound mole of oxyethylatedglycerol (1 to D 15 ratio) prepared in the manner previously describedis treated with one pound mole of maleic anhydride and heated atapproximately C. for-approximately thirty minutes to two hours, withconstant stirring, so as to yield a monomaleate.

'CXYETHYLATED GLYCEROL MALEATE Example 2 v The same procedure isfollowed as in the preceding example, except that two moles of malelcanhydride are employed so as to obtain the dimaleateinstea'd of themonomaleate.

and the like.

O'XYETHYLA'IED GLYoERoL MALEATE Example 3 The same procedure is followedas in the two preceding examples, except that three moles of maleicanhydride are employed so as to obtain the trimaleate.

OXYETHYLATED GLYCEROL MALEATE Example 4 The same procedure is employedas in the preceding examples, except that oxyethylated glycerol (ratio 1to 18) is substituted in place of oxyethylated glycerol (ratio 1 to 15).

OxxE'rHYtA'rEn GnLYcERoL MALEATE A Emmpleb The same procedure isemployed as in the preceding examples, except that oxyethylated glycerol(ratio 1 to 21) is employed instead of oxyet'hylated glycerol (ratio 1to 15) or (1 to 18) Previous reference has been made to an alcoholicbody which has been defined generically by theformula R1(0H)m. Thesub-generic class of alcoholic compounds employed as reactants in themanufacture of the present'compounds, are

hydroxylated acylated amides containing (a) an amino nitrogen-linkedacyl radical derived from a monocarboxy acid having not more than 5carbon atoms; (b) an acyl radical der ived from a detergent-formingmonoc'arboxy acid having at least 8 and not more than 32 carbon atoms;

and (c) an alcoholiform hydroxyl radical.

Detergent-forming acids having at least 8 and not more than 32 carbonatoms are exemplified by fatty acids, naphthenic acids, abietic acids,oxidized paraflin or wax acids, or the like, or

by simple modiflcationsthereof which do not detract from the ability ofthe acid to combine with alkali to produce soap or soap-like materials.Patent No. 2,242,837, dated May 20, 1941, to Shields.

Thus, hydrogenated oleic acid, chlorinated naphthenic acid, orbrominated abietic acid will ,form such detergent-forming bodies withthe same ease as the parent materials themselves. The oxidized acidsobtained by blowing or oxidation of the acids or esters, aresatisfactory. Such acids have frequently bee'nreferred tocollectiveinstance, ricinoleic'acid, oleic acid, mixed fatty acidsderived 'from soyabean oil, rapeseed oil, sesame oil, cottonseed oil,corn oil, peanut oil, Fatty acids, such as lauric acid, myristic acid,palmitic acid,'and the like, may be employed.

- clude reactant, but may use some suitable derivative such as the acylchloride, the anhydride, the ester, or amide; i. e., any suitable formmay be used which is the functional equivalent in supplying the acylradical.

Suitable primary and secondary amines which maybe used as primaryreactants include the following hydroxylated types: diethanolaminemonoethanolamine, ethyl ethanolamine, methyl ethanolamine,propanolamine, dipropanolamine, propyl propanolamine, etc. Otherexamples incyclohexylolamine, dicyclohexylolamine, cyclohexylethanolamine, cyclohexyl .propanolamine, benzylethanolalmine,benzylpropanolamine, pentanolamine, hexanolamine, octylethanolamine,octadecylethanolamine, cyclohexanolethanolamine, etc.

If the low molal monocarboxy acid happens to be hydroxylated, as inthe'instance of glycolic ,acid, lactic acid, hydroxybutyric acid, andthe like, it is obvious that a hydroxylated'detergentforming acid, forinstance, ri'cinoleic acid, hydroxystearic acid, and the like, could beesterified therewith, i. with the hydroxyl group, which is part of thelow molal acyl radical; and under such circumstances the primary orsecondary As to oxidized petroleum acids, see U. S.

Needless to say, 'the acylatirm need not The low molal monocarboxy acidshaving not more than five carbon atoms'are exemplified by acetic acid,formic acid, lactic acid,,- propionic acid, butyric acid, hydroxybutyricacid, furoic acid, etc.

In regard to both thedetergent-forming acids and in regard to the lowmolal acids, it is obvious that one need not use the acid itself as aamine need not be hydroxylated. Under these circumstances one mightemploy compounds such 'as'amylamine, diamylamine, butylamine,dibutylamine, benzylamine, cyclohexylamine, etc.

Other suitable types of amines will be described subsequently. Forinstance, one may employ the type involving the presence of an etherlinkage, as, for example, the following:

02114002114011 cznlo'olmon HN nN CIHlO czmou canon mNczmo canonSubsequently, reference will be made to U. S. Patent No. 2,238,929,dated April 22,1941, to Cahn and Harris. Momentarily attention isdirected to the numerous amino compounds, particularly secondaryhydroxylated amines there described. Such additional. amino compoundsare suitable as reactants, in view of what will be said subsequently.

Example A, Part (1), of. the aforementioned Cahn and Harris .patent willserve excellently as an initial illustration and is as follows:

Example A (1 224 grams of methyl acetate (3 moles) and 210 grams, ofdiethanolamine (2 moles) were mixed together, two layers forming atfirst, the mixture becoming a homogeneous mass after a short time.

had reacted. A portion of the reaction'mixture was subjected to a vacuumof .6 millimeters at 60 ,degrees C. in order to drive oil? the volatilematerial, namely, the unreacted methyl acetate and the methyl alcoholwhich was formed dur ing the reaction. The residue, upon titration,

showed a content of 4.64% of free diethanolamine. To 192.5 grams of thisresidue, 34.7 grams of methyl acetate were added and the mixture wasrefluxed for 3% hours. The resulting reaction product was then freedfrom its' low boiling constituents; namely, the methyl alcohol andun'reacted' 'methylacetate', by maimtaining the mass at "70 degrees C.under a pressure of 6 millimeters.

The mixture was refluxed for 19 hours, at which time of thediethanolamine The residue contained approximately. 0.8% of unreacteddiethanol amine, based upon a determination of the alkalinity of saidresidue by titration. The productwas a light yellow colored syrup,soluble in water, and contained a compound which was essentially theacetic acid amide of diethanolamine, having the following formula:

cimon CHa-C-N CZHiOH Having obtained a material of the kind abovedescribed, it is obvious that one can then esterify the material witheither one or two moles of a detergent-forming monocarboxy acid, so asto obtain a hydroxylated derivative. Obviously, if

- the detergent-forming acid employed does not contain an alcoholichydroxyl radical, for instance, if it is of the type otherthan thatxemplified by ricinoleic acid, hydroxystearic acid, and the like, thenone can only esterify one mole of such detergent-forming acid with acompound of the kind above described, for the reason that there must bea residual alcoholiform hydroxyl radical. If, however, an acid such asricinoleic acid, hydroxystearic acid, or the like is employed, then, ofcourse, two molesof such detergent-forming acid can be employed.Similarly, if desired, one

might esterify one hydroxyl with oleic acid, and

the other hydroxyl with ricinoleic acid.

following type which may be used for reaction with a detergent-formingacid:

Another suitable raw material is monoglycerylamine, as indicated by thefollowing formula:

H /OH N-CaHt H Attention is directed to the aforementioned Cahn andHarris patent, insofar that it illustrates a large number ofintermediate products which may be utilized to produce various finalcompositions of matter, as, for example, sulfated orsulfonatedderivatives, as contemplated in said aforementioned U. S. Patent No.2,238,929. However, the intermediate materials there described obviouslycan be used as alcoholic bodies in the preparatiorrof compounds of thetype herein con- If the experiment above described is repeated,

using monoethanolamine in the equivalent amount, then the final productis characterized by the following formula:

CsHiOH CHa-C-N The limitations in regard to the above type of compoundis perfectly obvious. Unless one can produce a secondary amide, which isdiflicult, and generally speaking, not particularly feasible, one must,of necessity, esterify with a hydroxylated detergent-forming acid, suchas ricinoleic acid, hydroxystearic acid, or the like.

If, however, instead of using acetic acid, one uses lactic acid or someother hydroxylated low molal carboxy acid, then the two formulas above'described change to the following forms:

The presence of this additional hydroxyl offers additional opportunityfor reaction and further elaboration is not necessary, except perhaps,to point out that even a type of material such as the following:

*alkyl oncngo-m alkyl might be employed, providedthat ricinoleic acid,

for example, is esterifled with the hydroxyl of the low molalmonocarboxy acid acyl group. Other variants too numerous to mentionsuggest themselves, as, for example, derivatives oftris(hydroxymethyl)arninomethane or similartypes of compounds, such asan amide of the templated. Such materials as there described are largelyderivatives of hydroxylated secondary amines; but for the purposesherein contemplated, such limitation does onot exist, in view of whathas already been said.

By way of illustration, the following examples will serve:

HYDROXYLATED Amos TYPE Inrnamsnmra Ezample 1 One pound mole of an. amideof the following formula:

H CHIC-LN/ I (hHiOH is reacted with one pound mole of ricinoleic aciduntil esterification is complete. Such esteriflcation reaction can beconducted by any one of the conventional means, usually heating at atemperature above the boiling point of water; for instance, 1l6-160 C.is suflicient. In some cases it may be desirable to pass a dried inertgas through the reacting mass, as, for example, dried carbon dioxide ordried nitrogen. Sometimes the reaction is extended by the presence of asmall amount of a sulfonic acid as a catalyst, for instance, of toluenesulfonic acid. In other instances, esterification may be conducted inthe .presence of an inert solvent,-such as xylene, which is permitted todistil off carrying water vapor .with it. The vapors are condensed,separation of water and xylene permitted totake place, and the xylenereturned to the reacting vessel while the water is diverted to asuitable draw-01f connection.

Hrnnoxrmran Amos TYPE Imsmnnm:

Example 2 ride. The product consisted essentially of a compound havingthe following formula:

CIHiOH CHIC-N\ o CZHk-O-fi-CuHtS o The above directions aresubstantially as they appear in Part (2) of Example A in theaforementioned Cahn and Harris patent. Previously,-

reference has been made to the same patent in regard to the manufactureof the acetic acid amide of diethanolamine, referred to as Part (1)hereof in the foregoing.

HYDROXYLATED AMInE TYPE INTERMEDIATE Example 3 The same procedure isfollowed as in Example 2, except that ricinoleic acid is substituted forlauric acid.

HYDROXYLATED AMIDE TYPE INTERMEDIATE Example 4 I The same procedure isfollowed as in Example lauric acid.

2, exceptthat naphthenic acid is substituted for HYnRoxYLATEn AMInE TYPEIN ERMEDI TE Example 5 The same procedure is followed as in Example 2,except that abietic acid is substituted for l'auric acid in Example 2.

HvnRoxYLAT n AMIn TYPE INTER E IATE Example 6 Theacetic acid amide oftris(hydroxyethyl)- aminomethane, previously described, is substitutedfor the acetic acid amide of diethanola- I mine, in Examples 2-5,preceding.

CoMPLETEn MoNoMERIc DERIVATIVE 1 Example 1 One'pound mole or a productof the kind described under the heading Oxyethylated' glycerol hmaleate,'Example 1 is reacted with one pound mole of Hydroxylatedamidetype intermediate, Example 3," preferably'in the absence of any highboiling hydrocarbonpr inert solvent. However,

a if an inert vaporizing solvent is employed, it is "generally necessaryto use one which has a higher boiling range than xylene,-andsometimesre- 1 oval ofsuch solvent might'present a difficulty.

In other'instances, however, suchh ghbOlllIlg inert vaporizing solvent,ifemployed, might be permitted to remain-in the reacted mass and appearas a constituent or ingredient of the final product. In any event, ourpreference is to conduct the reaction inthe absence of any such" solventand permit the reaction to proceed with the elimination of water. -Thetemperature of reaction is about 180 to200 C. and tion about 20 hours.

" COMPLETED MONOMERIC DERIVATI IVE time of reac.

The same'procedure is followed as in Completed monomeric derivative,Example 1, preceding, ex-. cept. that the dimaleate described under theheading Oxyethylated glycerol maleate, Example 2 is used instead of themonomaleate.

\ phthalate.

COMPLETED MoivoMERIc DERIVATIVE Example 3 The'same procedure is followedas in the two preceding examples, except that the trimaleate issubstituted for the monomaleate or dimaleate "in the two precedingexamples.

COMPLETED MoNoMERIc DERIVATIVE Example 4 The same procedure is followedas in Examples 2 and 3,-immediately preceding, except that for eachpound mole of the maleate, or each poundmole of the trimaleate, insteadof using one pound mole of hydroxylated ester amide of I the kindemployed in Examples 1 to 3, preceding as a reactant, one employs twopound moles.

COMPLETED MONOMERIC DERIVATIVE Example 5 The same procedure is followedas in Example I 3, preceding, except that for each pound mole oftrimaleate, instead of adding one pound mole of hydroxylated ester amideof the kind employed in Examples 1 to 3, preceding, one adds three poundmoles "of hydroxylated ester amide of the A kind employed in Examples 1to 3 for reaction.

COMPLETED Mo VoMERIc DERIVATIVE Emample't'. Referenceto the precedingexamples will show that -in each and every. instance oxyethylatedglycerol (ratio 1 to 15) has been employed as a raw materialor primaryreactant. 'In the present instance, a more'highl-y oxyethylated glycerolis employed, to wit, one involving the ratio of 1 to 18. (See'Oxyethylated glycerol maleate, Example 4, preceding.) I

CoMP ETEi)" MopoMERIc. DERIVATIVE Example 7 The same procedure isfollowed as Example 2 6, immediately preeedingexcept that theoxyethylated glycerol employed represents one havling an even higherdegree of oxyeth'ylation For example one indicated by the. ratio of lfto 21.

. (See Oxyethylated glycerol maleate, Example 5,

precedingJfl. v v 4 COMPLETED MoNoMERIc DERI A IVE Example 81 I V Thesame procedure is followed as in Examples 1 to 7, preceding,exceptthatinstead of employing a reactantuof the kind described underthe heading Hydroxylated amide type intermediate, Example 3,? oneemploys instead a reactant of the kind described under. the headingHydroxylated amide type intermediate, Example 6.

The method of producing such fractional esters 1 is well-known. Thegeneral procedure is to emp1oy a; temperature above theboilingpoint ofwater and below the pyrolytic-point of the reactantsa The productsare'mixed and stirred conreadily in the presence of an inert solvent,that carries away the water of esterification which may be formed,although as is readily appreciated,

' such water of esterification is absent when such present and employedto carry off the water formed. The mixture of xylene vapors and watervapors can be condensed so that the water is separated. The xylene isthen returned to the retives of both the polymers and esterificationmonomers, separately and jointly. Although the class of materialsspecifically contemplated in this instance is a comparatively small andnarrow class of a broad genus, yet it is obviously impossible to preventany adequate formula which would contemplate the present series in theircomplete ramification, except in a manner employed in the heretoappended claims.

Although the products herein contemplated vary so broadly in theircharacteristics, i. e., monomers through sub-resinous polymers,soluaction vessel for further circulation. This is a conventional andwell-known procedure and requires no further elaboration.

In the previous monomeric examples there is a definite tendency, inspite of precautions, at least in a number of instances, to obtainpolymeric materials and certain cogeneric by-products. This is typical.of course, of organic reactions of this kind, and as is well known,organic reactions per so are characterized by the fact that 100% yieldsare the exception, rather than the rule, and that significant yields aresatisfactory, especially in those instances where the byproducts orcogeners may satisfactorily serve with the same purpose as the principalor intentional product. This is true in the present instance. In manycases when the compound is manufactured for purposes of demulsification,one is better oi! to obtain a polymer in the sense previously described, particularly a polymer whose molecular weight is a rather smallmultiple of the molecular weight of the monomer. For instance, a polymerwhose molecular weight is two, three, four, five, or six times themolecular weight of the monomer. Polymerization is hastened by thepresence of an alkali, and thus, in instances where it is necessary I tohave a maximum yield of. the monomer, it may be necessary to take suchprecautions that the alkali used in promoting oxyethylation of glycerol,be removed before subsequent reaction. This, of course, can be done inany simple manner by conversion to sodium chloride, sodium sulfate, orany suitable procedure.

In the preceding examplesof the Completed monomeric derivative, Examples1 to 10, inclusive,

no reference ismade to the elimination of such alkaline catalyst, inview of the efiectiveness of the low multiple polymers as demulsifiers.Previous reference has been made to the fact that the carboxylichydrogen atom might be variously replaced by substituents, includingorganic radicals, for instance, the radicalsobtained from alcohols,hydroxylated amines, non-hydroxylated amines, polyhydric alcohols, etc.Obviously, the reverse is also true, in that a free hydroxyl group maybe esterified with a selected acid, varying from such materials asricinoleic acid to oleic acid, including alcohol acids, such ashydroxyacetic acid, lactic acid, ricinoleic acid and also polybasicacids of the kind herein contemplated.

With th above facts in mind, it becomes obvious that what has beenpreviously said as to polymerization, with the suggestion thatbyproducts or cogeneric materials were formed, may be recapitulated withgreater definiteness, and one can readily appreciate that the formationof heat-rearranged derivatives or compounds must take place to a greateror lesser degree. Thus, the products herein contemplated may becharacterized by-being monomers of the type previously described, oresterification polymers, or the heat-rearranged derivatives of the same,

and thus including the heat-rearranged derivable products,water-emulsifiable oils or compounds, hydrotropic materials, balsams,subresinous materials, semi-resinous materials, and the like, yet thereis always present the characteristic unitary hydrophile structurerelated back to the oxyalkylation, particularly the oxyethylation of theglycerol used as the raw material. As hereinafter indicated, in theresolution of oil field emulsions, the demulsifier may be added to theemulsion at the ratio of 1 part in 10,000, 1 part in 20,000, 1 part in30,000, or for that matter, 1 part in 40,000. In such ratios it well maybe that one cannot differentiate between the solubility of a compoundcompletely soluble in water in any ratio, and a, semi-resinous productapparently insoluble in water in ratios by which ordinary insolublematerials are characterized. However, at such ratios the importance mustreside in interfacial position and the ability to usurp, preempt, orreplace the interfacial position previously occupied perhaps by theemulsifying colloid. In any event, reviewed in this light, the obviouscommon property running through the entire series, notwithstandingvariation in molecular size and physical make-up, is absolutelyapparent. Such statement is an obvious oversimplification of therationale underlying demulsification, and

COMPLETED POLYMERIC Dsnrva'rrvns INcLUnmc HEAT-REABRANGED CocmmasExample 1 A polyfunctional monomer selected from one of those describedunder the heading Completed monomeric derivatives, Examples 1 to 7,inclusive, is heated at a. temperature of approximately 220-240 C., withconstant stirring, for a period of 2-60 hours, so as to eliminatesuflicient water, in order to insure that the resultant product has amolecular weight approximately twice that of the initial monomer.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED Cos-suresExample 2 ing a molecular weight of approximately three to four timesthat of the initial product.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED COGENERSExample 3 The same procedure is followed as in Examples which is stickyor sub-resinous in nature.

1 to 2, preceding, except that the polyfunctional monomer is selectedfrom the kind described ative, Example 8, instead of from Example 7.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED COGENERSExample 4 a mixture'oi" materials of the kind described in Completedmonomeric derivative, Example 3, and

infiompleted monomeric derivative, Example 4, are mixed in molecularproportion and subjected to polymerization in the manner indicated in'the previous examples. 4

It is understood, of course, that the polymerized product need 'notbe.obtained as a result of a twostep procedure.v In other words, one neednot convert the reactants into the monomer and then subsequently convertthe monomer .into the polymer. The reactants may be converted throughthe monomer to the polymer in one step. Indeed, the formation of themonomer and polymerization may take place simultaneously. This isespecially true if polymerization is conducted in the I under theheading Completed monomeric deriv-'- absence of a liquid such as xylene,as previously described, and if one uses a comparatively highertemperature, for instance, approximately 220 C. for polymerization..Thus, one pound mole of an oxyethylated glycerol polymaleate is reactedwith one mole of a material of the kind'described under the-headingI-iydroxylated amide type intermediate, Example 3 for approximately 20hours at a temperature of about 220 C. until the mass is homogeneous.It. is stirred constantly during reaction. Polyfunctionality may residein deahydration (etherization) of twohydroxyl groups .attached todissimilar molecules.

The fact that the polymerized and heat-reap ranged products-can bemadein a single step, il-

= 'lustrates a phenomenon which sometimes occurs either in suchinstances where alcoholic bodies of the kind herein illustrated arecontemplated as reactants, or where somewhat kindred alcoholic bodiesare employed. The reactants may be mixed mechanically to give ahomogeneous mixture, or if the reactants do not mix to give ahomogeneous mixture, thenearly in the .re-

action stage there is formed, to a greater. or lessen.

degree, suflicient monomeric materials so that a homogeneous system ispresent.- Subsequently, as reaction continues, the system may become Iheterogeneous and exist in two distant phases, .one being possibly. anoily body of moderate viscosity, and the other being a heavier material,

many instances it will be found that the-thinner liquid material is amonomer and the more viscous. or resinous material is a polymer, as-.

previously described. Such product can be used for demulsificationbyadding a solvent which will mutuallvd ssolve the two materials, orelse, by separating the two heterogeneous phases and employing each as.if it were a separate product of reaction. v

Conventional demulsifying agents employed in the'trcatment of oil fieldemulsions are used as such, or after dilution with any suitable solvent,such as water; petroleum hydrocarbons such as gasoline, kerosene, stoveoil, a coal tarproduct such as benzene, toluene, xylene, tar acid oil,cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols,such as methyl alcohol, ethyl alcohol, denatured alcohol, propylalcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may beemployed as diluents. Miscellaneous'solvents', such as pine-oil, carbon'tetrachloridesulfur dioxide extract obtained in the refiningof petroleum, etc., may be employed as diluents.

larly, the material or materials hereindescribed,

Simiwhen employed as demulsifiers forJwater-in-oil emulsions, may beadmixedwith one or more oi the solvents customarily used in connectionwith conventional demulsifying agents, provided that such compounds are.compatible. They will be compatible'with the hydrophile type of solventMoreover, said material or ing agents may be used in a water-solubleform, or in an oil-soluble form, or in a form exhibitingboth oil andwater-solubility. Sometimes they may be used iir ai form which exhibitsrelatively limited oil-solubility. However, since such. re- I agents aresometimes used in a ratio of 1 to 10,000, o r 1 to 20,000, or even 1 to30,000, such an I apparent insolubility in oil and water is notsignificant, because said reagents undoubtedly have solubility withinthe concentration employed. This same fact is true in regard to thematerial or materials herein described, except that they are invariablywater-soluble.

We desire to point out that the superiority of the reagent ordemulsifying agent contemplated in our herein described process forbreaking petroleumemulsions, is based ,upon its ability to treat certainemulsions more advantageously and at asomewhat lower cost than ispossible with other available demulsifiers, or conventional mixturesthereof. -It is believed that the particular demulsifying agent ortreating agent herein described will find comparatively limitedapplication', so far as the majorityof oil field emulsions areconcerned; but we have foundthat such a demulsifyingagent has commercialvalue, as it will economically break or resolve oilfield emulsions in a,number of cases which cannot be In practising our improved process forresolving petroleum emulsions" of thewwater-in-oil type, a treatingagent or demulsifying agent of the kind above described isb'rought intocontact with or caused to act .upon the emulsion to be treated, in anyof .the various ways, or by any of the various apparatus now generallyused to resolve or break petroleum emulsions with a chemical reagent,the above procedure being used either alone, or'in combination withother demulsifying procedure, such, as the electrical dehydrationprocess. I

The demulsifier herein contemplated may-"be employed in connection withwhat is commonly known as down-the-hole procedure, i. .e., bringin thedemulsifier in contact with the fluids of the well at the bottom of thewell, or atsome point prior to their emergence. This particular type ofapplication is decidedly feasible when the demulsifier is used inconnection with acidification. of calcareous oil-bearing strata,especially if suspended inor dissolved in theacid employed foracidification. I

Cognizance must be taken of the fact that the surface of the reactingvessel may increase or decrease reaction rate and degree ofpolymerization, for instance, an iron reaction vessel speedsvethylenecliamine,

Patent is:

up reaction and polymerization, compared with glass-lined vessel.

As has been previously indicated, the sub-genus employed as an alcoholin the present instance is one of a series of alcoholic compounds whichare contemplated in our co-pending application Serial Nos. 447,151,447,152, 447,153, 447,154, 447,- 155,-447,156, 447,157, 447,158,447,159, 447,160, 447,-

161,447,162, 447,163, 447,164, 447,166, 447,167 and 447,168, filedJunel5, 1942.

It is to be noted that in such instances where v the alcoholic bodycontains a reactiveamino hy-,

drogenatom, ior instance, in *the case where an acylated hydroxylatedpolyamine is employed, for example, the ricinoleyl acid ester ofhydroxyethyl the oxyethylated glycerol maleate might react to form anamide of-maleic acid. In such instances, of course, such type, to wit,the amido type, is contemplated within th scope of the appended claimsin the particular instance. but elaboration is eliminated, because it isunnecessary and would only incur greater length of descriptive matter.stated in another way, in all appropriate instances, the expressionesterification polymers in the appended claims, includes amidiflcationpolymers, as well as esteriflcation polymers.

Having thus described our invention, what we claim as new and desire tosecure. by Letters 1. A process for breaking petroleum emulsions of thewater-in-oil type, characterized by subjecting the emulsion to theactionof a demulsifier comprising a member of the class consisting of-monomers, sub-resinous esteriflcation polymers,

and cogeneric sub-resinous heat rearranged derivatives of the monomersand aforementioned polymers, separately and jointly, and of thefollowingformula:

lwflnao)" OOGMCO02mlz CaHaOr-[(C HwO) M in which R is the carboxyl-freeradical of a polybasic carboxy acid having not over 8 carbon atoms; 81is a hydroxylated acylated amide radi-' (ml containing: (a) an aminonitrogen-linked acyl radical of a monocarboxy' acid having not overcarbon atoms; and (b) an acyl radical derived of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifiercomprising a member of the class consisting of monomers, sub-resinousesteriflcation polymers,

and cogeneric sub-resinous heat-rearranged derivatives of the monomersand aforementioned polymers, separately and jointly, and of thefollowing formula;

[(cnnrnmn-oooaooozl, CaH508' [(CnH2n )nH]I ucnmnowooonooom.

.ing: (a) an in which a is a carboxyl-free radical of a dibasic carboxyacid having not over 6 carbon atomsrRi is a hydroxylated facylated amideradical containor a monocarboxy acid having not over 5 carbon atoms; and(b) an acyl radical derived from a detergent-forming monocarboxy acidhaving at .least 8 and not more than 32 carbon atoms; Z is anacidichydrogen atom equivalent including the acidic hydrogen atomitself; n represents the numerals 2 to 4; n represents the numerals 3 to10; 3: represents the numerals 0 to 2; 1 represents the numerals 0 to 2;and 2 represents the numerals 1 to 3.

3. A process forbreaking petroleum emulsions of the water-in-o'il type,characterized by subjecting the emulsion to the action of a demulsifiercomprising a member of the class consisting of monomers, sub-resinousesteriflcation polymers, and cogeneric sub-resinous heat-rearrangedderivatives-of the monomers and aforementioned polymers, separately andjointly, and of the following formula 1' least 8 and not[(CaHlDhQbC-RCOOZL Cantos-Renown],

(C3HIO)IOOCRCOOB1]| in which R is a carboxyl-free radical of a dibasiccarboxy acid having not over 6 carbon atoms; R1 is ahydroxylatedacylated amide radical containing: (a) an aminonitrogen-linked acyl radical of a monocarboxy acid having not over 5carbon atoms; and (b) an acyl radical derived from a detergent-formingmonocarboxy acid having at more than 32-canbon atoms; A is an acidichydrogen atom equivalent including the acidic hydrogen atom itself; nrepresents the numerals 3 to 10;:1: represents the numeralsl) to 2; 11represents the numerals 0 to 2; and z represents the numerals 1 to 3.

4. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subject-'- polymers, separately and jointly, and of thefollowing formula:

I [(CrHrOhuOOCRCOOZ],

CaHsO r-KCaHl NH]! cmrowoocrzooonq.

in which R is a carboxyl-freeradical of a dibasic carboxy acid havingnot over 6 carbon atoms; R1 is whydroxylated acylated amide radicalcontaining: (a) an amino nitrogen-linked acyl radical of a monocarboxyacid having not-over 5 carbon atoms; and (b) an acyl radical derivedfrom a detergent-forming monocarboxy acid having at least 8 and not morethan 32 carbon atoms; Z is an acidic hydrogen atom equivalent includingthe acidic hydrogen atom itself; n represents the numerals 3 to 10;;1:represents the numerals 0 to 2; 11 represents the numerals 0 to 2; and zrepresents the numerals lto 3. I

5. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifiercomprising a polar acidic member of the class reananged derivatives ofthe monomers and amin'o nitrogen-linked .acyl radicalaforementionedpolymers, separately and jointly, and of,the following formula:

' lwinioxvoooao0oz z CaHrOz[(CzH4O) H],

[(CzH4O),.'0OCRCO0R1], inwhich R is a carboxyl-free radical of a dibasiccarboxy acid having not over 6 carbon atoms; R1 is ahydroxylatedacylated amide radical containing: (a) an aminonitrogen-linked acyl radical of a monocarboxy-acid having not overcarbon atoms; and (b) an acyl radical derived from a detergent-formingmonocarboxy acid having at least 8 and not more than 32 carbon atoms; Zis an acidic hydrogen atom equivalent including the acidic hydrogen atomitself; n represents the numerals 3 to 10;" :0 represents the numerals 0t0 2; 11/ represents the numerals 0 to 2; and 2 represents the numerals1 to 3.

6. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifiercomprising a polar acidic member of the class consisting of monomers,sub-resinous esterification polymers, and .cogeneric sub-resinousheatrearranged derivatives of the monomers and aforementioned polymers,separately and Jointly, and of the following formula:

' 'KCSHKDMOQQRCOOZ], CaHsOrKCrHAOh H],

v [(mmonoocncooam in which R is a carboxyl-free radical of a dibasiccarboxy acid having not over 6 carbon atoms; R1

is a hydroxylated acylated amide radical containasaa'ros' teriflcationpolymers, and cogeneric sub-resinous heat-rearranged derivatives of themonomers and aforementioned polymers, separately and jointly, and ofthefollowing formula:

' in which R is a carboxyl-free radical of a dibasic ing: (a) an aminonitrogen-linked acyl radical of a monocarboxy acid having not ,over 5carbon atoms; and (b) an acyl radical derived from a higher fatty acidhaving at least 8 and not more than 32 carbon atoms; Z- is an acidichydrogen atom equivalent including the acidic hydrogen atom itself nrepresent the numerals 3 to 10; :1:

represents the numerals 0 to 2; 9 represents the numerals Q to 2; and-zrepresents the numerals carboxy acid having not over 6 carbon atoms; R1is a hydroxylated acylated amide radical containing: (a) an aminonitrogen-linked acyl radical of a monocarboxy acid having not over 5carbon atoms; (b) an acyl radical derived from a higher fatty acidhaving 18 carbon atoms;' Z is an acidic hydrocarbon atom equivalentincluding the acidic hydrogen atom itself; n represents the numerals 3to 10; a: represents the numerals 0 to 2; 3/ represents the numerals 0to 2; and 2 represents the numerals 1 to 3. v

8. A process for breaking petroleum emulsions of the water-in-oil type,characterized by sub- Jecting the emulsion to the action of ademulsifier comprising a polar acidic member of the class consisting ofmonomers, sub-resinous esterification polymers, and cogenericsub-resinous heatrearranged derivatives of the monomers andaforementioned polymers, separately and Jointly, and of the followingformula:

|;(c:Hi,0)..'oooRcooz cantor-Ramona [(011140) '0 O 0 RC 0 QRilr in whichR is a carboxyl-free radical of a dibasic'

